Ethylene polymer composition for blow molding

ABSTRACT

Polyethylene blends for blow molding processes are disclosed, comprising from 12 to 25 weight percent of high molecular weight component, 5 to 83 weight percent of a medium molecular weight component, and 5 to 83 weight percent of the low molecular weight component, wherein the ratio of high molecular weight to medium molecular weight is greater or equal to 1.7 and the ratio of medium molecular weight to low molecular weight is greater or equal to 1.7, and wherein the blend has a melt index in the range of 0.01 to 2.0.

This is a division of application Ser. No. 508,696 filed June 28, 1983,now U.S. Pat. No. 4,525,322.

This invention relates to ethylene resin compositions particularlysuitable for blow molding applications. More particularly, thisinvention relates to ethylene polymer compositions and process forpreparing such compositions in the obtaining of a polymer particularlysuited for intermittent blow molding applications.

Polyethylene characteristics required for molding useful articles andthe like vary depending upon the method of molding and the end use towhich the material is to be put. As is known in the art, variousproperties of polymers must be designed to fit particular moldingprocesses and designed to withstand the end use to which the product ofthe process is to be put.

It is well known that polymers having low molecular weight together witha narrow molecular weight distribution are suitable for articles moldedby injection molding processes. In contrast, blow molding processesrequire polymers having relatively high molecular weights and broadmolecular weight distributions.

Polymers utilized for these purposes must provide excellent physicalproperties with regard to the balance of stiffness and environmentalstress cracking resistance (ESCR) as well as esthetics such as color,top load (or stacking ability) while providing strength and chemicalresistance with a low wall thickness.

While many polymers have been produced to fulfill these desirablecharacteristics, normally such polymers have severe faults whichcontinually plague production processes. Polymers produced by mixinghigh molecular weight polyethylenes with low molecular weightpolyethylenes, while providing many desirable characteristics, generallyhave lower die swell, lower melt tension and produce large amounts ofgels or faults during molding.

In blow molding processes, bottles are formed from cylindrical moltenpolymer tubes extruded from a machine, each of which have a lengthsuitable for the ultimate application. These extruded cylinders arecalled "parisons".

In continuous blow molding applications, the parison is continuouslybeing extruded at a constant rate. On the other hand, the intermittentblow molding process involves the collection of molten polymer in areservoir inside the machine followed by the rapid extrusion of theparison by a ram. While the parison is extruded from a continuous blowmolding machine over the entire cycle time of the previous articlemolded, the intermittent blow molding machine extrudes the parison in asmall fraction of the cycle time.

The parison is extruded more rapidly in intermittent blow molding thanit is in continuous blow molding; consequently, the shear rates that areencountered by polymers in intermittent blow molding are much higherthan they are in continuous blow molding.

In both cases, after the mold has retrieved the appropriate length ofthe parison, air is injected into the inside of the mold which forcesthe molten polymer against the mold to form the article. After thepolymer has cooled to form the article, the mold opens, ejects thefinished article and retrieves a fresh length of parison to repeat thecycle.

The physical property advantages inherent in the resins of the presentinvention in products made by intermittent blow molding processes willalso be present in continuous blow molding. However, the processingproperty advantages observed in intermittent blow molding applications,which require much more closely controlled processing properties, areless evident in the continuous extrusion processes.

Thus it can be seen that polyethylene consumers use many differentgrades of polyethylene to meet various product requirements. Usually,polyethylene produced by mixing high molecular weight and low molecularweight polyethylene has low die swell. As a result, materials made fromthese polymers have a low wall thickness. Low gel levels in such lowwall thicknesses become increasingly important, since a gel is adiscontinuity in a normally uniform surface. Thus, the balance ofproperties such as low gels, proper die swell, high ESCR, topload andesthetics is normally very difficult to obtain, since a gain in one areameans a corresponding loss in other areas.

It would therefore be of great benefit to provide a polymer compositionwhich is suitable for blow molding applications which provide advantagesin critical polymer property areas while substantially maintainingdesirable polymer processing properties.

We have now discovered that a polyethylene blend particularly suitablefor intermittent blow molding applications and providing good die swell,low gel content and high extrusion rate, together with polymer stabilitycan be obtained from polyethylene resins prepared from Ziegler/Nattacatalysts containing high molecular weight, medium molecular weight andlow molecular weight fractions, wherein the resin comprises (a) a highmolecular weight component with a viscosity average molecular weight(H-MW) ranging from about 590,000 to about 860,000, and preferably from660,000 to 775,000, and comprising from about 12 to about 25% by weightof the total resin; (b) a medium molecular weight component having amolecular weight (M-MW) from about 75,000 to about 600,000 andcomprising from about 5 to 83% by weight of the total resin; (c) a lowmolecular weight component having a molecular weight (L-MW) from about10,000 to about 100,000 and comprising from about 5 to about 83% byweight of the total resin, wherein (d) the ratio of ##EQU1## is greaterthan or equal to 1.7 and the ratio of ##EQU2## is greater than or equalto 1.7 and wherein the density of the total resin is from about 0.940 toabout 0.970 and the melt index at a 2.16 kilogram load of the totalresin is from about 0.01 to about 2.0.

The resin described above comprises polyethylene homopolymer and/orpolyethylene copolymers in any fraction wherein the copolymer is formedfrom ethylene and a comonomer containing from 3 to 12 carbon atoms.

Attempts have been made to produce ethylene polymers which provideproperties as described. Representative but non-exhaustive examples ofsuch references are U.S. Pat. No. 4,336,352 which deals with threecomponent polyethylene serials. This patent teaches that the highmolecular weight component cannot exceed 10% by weight of the polymer.However, this resin has a severe disadvantage in low extrusion rates,since the limitation on high molecular weight component largelydecreases the rate of material which can be extruded uniformly. JapaneseKokai 57-141409 discloses a three component process which has a highmolecular weight component ranging up to over 50% of the total resincomposition. However, tests have shown that the molecular weight of thehigh molecular weight component of this particular blend is so high thatgels become a problem and thin wall bottles become difficult to producewith any degree of uniformity.

During the intermittent blow molding process, the extruded parison tendsto swell in both the outer dimension and the wall thickness. Thisswelling has been termed in various places die swell, the Barus effectand the memory effect. We refer to this phenomenon of the swelling ofthe outer dimension as flare swell and to the swelling of the wallthickness as weight swell.

These are certain desirable levels of flare swell and weight swell forintermittent blow molding resins. One fault of earlier two componentsamples of Ziegler/Natta resins reported in the literature (U.S. Pat.No. 4,336,352) is that the weight swell was too low. In addition, theextrusion rate at high shear rates was also inadequate, leading tolowered moldability.

The present invention provides a composition and a method capable ofovercoming these processing faults. In addition, the compositiondescribed herein yield resins with superior physical properties withZiegler/Natta resins as compared to conventional chromium based blowmolding resins. The environmental stress cracking resistance (ESCR),impact strength and topload strength are far superior to many commercialresins. These samples, in general, show a superior impact strength atcomparable topload values. Conversely, if ESCR values are held constant,the topload strength of these resins is superior to conventional blowmolding resins. A process for producing these compositions is alsodisclosed.

Processes for producing polyethylene in multi-step polymerizations arewell known. U.S. Pat. No. 3,392,213 teaches utilization of the samecatalyst in multiple reactors in order to produce higher molecularweight polymers. U.S. Pat. No. 4,357,448 shows a two-step process forpolymerizing ethylene. These patents are only representative of the manyin the art which teach such processes and suitable Ziegler/Nattacatalysts for producing such materials.

However, the present invention consists of a blend of three polyethylenecomponents, each containing, respectively, high molecular weight, mediummolecular weight and low molecular weight fractions, each componentselected from the group consisting of ethylene homopolymers andcopolymers of ethylene and an olefin having from 3 to 12 carbon atoms.The high molecular weight fraction comprises from 12 to 25 percent,preferably from 16 to 22 percent by weight of the total resin and has amolecular weight (H-MW) ranging from about 590,000 to about 860,000, andpreferably from 660,000 to 775,000.

The medium molecular weight component comprises from about 5 to 83percent by weight, preferably from about 20 to 35 percent by weight ofthe total resin and has a molecular weight (M-MW) from about 75,000 toabout 600,000.

The low molecular weight component comprises from about 5 to about 83percent by weight, preferably from about 43 to about 64 percent byweight of the total resin and has a molecular weight (L-MW) from about10,000 to about 100,000. It is necessary that the ratio of high tomedium molecular weight components be greater than or equal to 1.7,while the ratio of medium to low molecular weight components be greaterthan or equal to 1.7. The density of the total resin must fall in therange of from about 0.940 to about 0.970 and the melt index as measuredby the ASTM-1238 method under a 2.16 kilogram load must range from about0.01 to about 2.0.

Utilizing the resins of the present invention it was unexpectedly foundthat the addition of more than 10% of the highest molecular weightcomponent did not drop the melt index to unacceptable levels, nor didthe measure of flowability (viscosity at 200 reciprocal seconds or 200sec⁻¹ hereinafter VIS200) rise to unacceptably high levels. It wasunexpectedly found that weight percents of the high molecular weightcomponent above 12% by weight, and preferably 16% by weight, of thetotal composition actually increased the flowability (lowered theviscosity) at higher shear rates at a constant overall blend melt index.Therefore the VIS200 value is a close approximation of the extrusionrate of the resin blend, such that a lower VIS200 value indicates ahigher extrusion rate can be expected. Thus it is apparent that thisparticular combination of resin components greatly improved processingproperties over those properties provided by resins of the prior art.

Utilizing the materials of the present invention in blow moldingapplications, melt strength can be enhanced by adding more than 12% ofthe high molecular weight component. Good melt strength is a known anddesirable property of blow molding resins. Weight swell of the threecomponent blend of the present invention can be increased as desired byaddition of high molecular weight components at levels greater than 12%.

Further, the uniformity of the resins of the present invention are atleast as good as those of the prior art wherein high molecular weightcomponents range from 0 to 10 percent by weight. This uniformity is notexpected from the teachings of the prior art as evidence by U.S. Pat.No. 4,336,352.

The method of preparing polyethylene blends of the present invention isnot critical so long as the target properties are acquired. The threecomponent blend can be prepared in reactors in series mode, reactors inparallel mode, or a combination of such modes. The series reaction isone in which the catalyst particles successively pass through three ormore reactors operating under different conditions in which the threecomponents are prepared and is the preferred method of the presentinvention. This results in polymer particles which, in general, containsome of each of the three components, and such a process is generallydescribed in U.S. Pat. No. 3,392,213.

Catalysts useful of the present invention are Ziegler/Natta catalysts,which provide excellent esthetic properties such as color and odor ascompared to chromium based catalysts, and which in the past have haddifficulty in matching the processing properties of resins producedusing chromium based catalysts. Ziegler/Natta catalysts are described indetail in Ziegler/Natta Catalysts & Polymerizations John Boor, Jr.,Academic Press, (1979). Suitable Ziegler/Natta catalysts and theZiegler/Natta catalysts used in all experimental results described inthis specification are described in U.S. Pat. No. 3,907,759; U.S. Pat.No. 4,223,118 and European Patent Application 68,200.

Resins of the present invention are most conveniently prepared in seriesmode reactors in which the total reaction medium is passed from reactorto reactor and the product recovered therefrom. Preferably catalyst isadded only to the first reactor.

The invention is more concretely described with reference to theexamples below wherein all parts and percentages are by weight unlessotherwise specified. The examples are provided to illustrate the presentinvention and not to limit it.

The examples as presented contain certain symbols and terms as well asmethods for calculating values which are believed well known in the artbut which are described here for convenience.

MI₂ is melt index as measured according to ASTM D-1238 under a load of2.16 kilograms.

MI₂₀ /MI₂ denotes the quotient obtainable by dividing the value of themelt index measured under a load of 21.6 kilograms by the value obtainedmeasuring a melt index under 2.16 kilograms. MI₂₀ /MI₂ measures thebroadness of the polyethylene molecular weight distribution with largervalues implying broader molecular weight distributions.

The molecular weight of a component is calculated from the MI₂ data byway of the intrinsic viscosity. First, the melt indexes of thecomponents are converted into intrinsic viscosity values by using therelationship.

    Log (MI.sub.2)=1.5112-4.986×log [n].

This relationship was extablished by a linear regression analysis of aplot of Log (MI₂) versus Log [n] over a wide range of melt index values,producing an equation with the high correlation factor of 0.993.

The molecular weight of the component can then be calculated from theintrinsic viscosity value (either measured or calculated using themethod described above) by the equation mentioned in the Journal ofPolymer Science, volume 36, page 91 (1956) and used in U.S. Pat. No.4,336,352 namely,

    [n]=6.8×10.sup.-4 ×[MW].sup.0.67.

Weight swell refers to the thickening of the tube wall which occursafter passage of the polymer through an annular die. Flare swell refersto the increase in the diameter of the tube after being extruded throughan annular die. Flare swell percent and tube weights were measured onpolymer tubes extruded from an annular die at shear rates above theshear rate of oscillating flow. The tubes were collected at fourdifferent shear rates. The flare swell percent at each shear rate iscalculated by ##EQU3## wherein Dextrudate is the average tube diameterand Douter is the outer diameter of the annulus. The tube weight isreported as the weight in grams of a 31/2 inch length. A reported flareswell percent and tube weight values are obtained from a linear leastsquare fit of the four measured swell properties vs shear rate. Theflare swell percent (FSP) and tube weight (TW) are the values obtainedat a certain rheometer piston velocity. These tests approximate theflare swell and weight swell observed in commercial processing.

All polymer tubes were produced using a Sieglaff-McKelvey capillaryrheometer interfaced to a Tektronix 4052 computer for data collectionand analysis. The rheometer was operated in a constant stress mode andmelt temperature was 190° C. for all measurements.

The melt viscosity of the resin blends is also measured in theSieglaff-McKelvey capillary rheometer. The above mentioned viscosity 200value (or VIS200) is the melt viscosity of the sample as measured onthis rheometer at a shear rate of 200S⁻¹.

Solution-mixed samples were prepared by dissolving polyethylene inhydrocarbon solvent at 140°-150° C., then precipitating the polymer andwashing it with isopropanol in a blender.

Melt-mixed samples are prepared in a Brabender Plasticorder™ or a HaakeRheocord Torque Rheometer™ by first stabilizing the resin and thenmixing the resin for a time range from 10 minutes to 1 hour.

Samples are roll-milled by first stabilizing the resin and then mixingon a roll mill operated with 70 pounds per square inch (psig) steam onthe hotter roll for 5-30 minutes.

The MI₂ of laboratory blends are calculated based on the composition ofthe blend according to the Journal of Polymer Science, Part A, Volume 2,pages 2977-3007, (1964) which was modified to yield the followingequation: ##EQU4## where H% percentage of the total composition is madeup by the high molecular weight component; M% is the percentage of thetotal composition which consists of the medium molecular weightcomponent; L% is the percentage of the total composition which consistsof the low molecular weight component; H-MI₂ is the melt index of thehigh molecular weight component; M-MI₂ is the melt index of the mediummolecular weight component; L-MI₂ is the melt index of the low molecularweight component. The equation was used to calculate the MI₂ values forthe laboratory blends made according to the present invention.

Three component polyethylene blends were prepared in series generallyusing the catalyst described in U.S. Pat. No. 3,907,759, U.S. Pat. No.4,223,118 and European Patent application 68,200 in the process of U.S.Pat. No. 3,392,213 and the U.S. Pat. No. 4,258,167.

Column crush properties (or topload strength) of bottles, made in anintermittent blow molding machine, are measured by ASTM method D2659 andare reported in pounds.

Drop impact strength of bottles made on an intermittant blow moldingmachine are measured by ASTM method D2463 and are reported in feetdropped.

Bottle stress crack resistance was measured by ASTM method D2561, exceptthat a slightly higher bottle pressure was used. The values reported areF 50 values and the units are hours. In this test, bottles from acontinuous blow molding machine were tested to improve thereproducibility of the test.

EXAMPLE 1

In general, the Ziegler/Natta catalyzed resins and chromium catalyzedresins show different properties with regard to flare swell percent,tube weight and VIS200. Desirable properties are moderate flare swellpercent values, a consistent high tube weight and a low VIS200. Table 1illustrates a catalyst-produced resin made using the catalyst systemdescribed in U.S. Pat. Nos. 3,907,759; 4,223,118 and European Patentapplication 68,200 and a commercially available chromiumcatalyst-produced resin, (Phillips 5502, trademark of and sold byPhillips Chemical Co.) A comparison of properties of these commercialresins are set forth below.

                  TABLE 1                                                         ______________________________________                                                   Flare Swell                                                                              Tube                                                               Percent    Weight  VIS200                                          ______________________________________                                        Ti-catalyst resin                                                                          43.9         1.04    1.08                                        Cr-catalyst resin                                                                          41.9         1.34    0.96                                        ______________________________________                                    

The results shown indicate that the titanium catalyzed resin isdeficient in weight swell properties as compared to the chromiumcatalyzed resin.

EXAMPLE 2

Resin blends were prepared in the laboratory by mixing three singlecomponent blends together to form a tri-component blend. The individualcomponents were prepared in laboratory reactors. The mixing was effectedby use of a roll mill as described above. Within pairs of samples thelow molecular weight melt index (L-MI₂) and the ratio of the mediumweight to low molecular weight percentages were held constant togetherwith the total blend melt index. The data showed that the weight swellfor the resins with more high molecular weight content was consistentlyhigher, while the VIS200 value is consistently lower, as compared toresins with lower high molecular weight content. Both of these changesare useful for producing blow molding resins having excellentproperties. The data is set forth in Table 2 below, wherein H-MI₂indicates the MI₂ value of the high molecular weight fraction.

                  TABLE 2                                                         ______________________________________                                        H %     H-MW         Tube Weight                                                                              VIS200                                        ______________________________________                                        14      860,000      1.46       1.06                                           6      860,000      1.16       1.30                                          14      860,000      1.46       1.20                                           6      860,000      1.26       1.40                                          14      860,000      1.40       1.05                                           6      860,000      1.15       1.15                                          14      860,000      1.48       1.15                                           6      860,000      1.24       1.26                                          ______________________________________                                    

In each case, the higher H% results in a higher tube weight value and alower VIS200 value. This would indicate that resins with higher tubeweight values (higher weight swell values) and lower VIS200 (enhancedextrusion rates) can be produced at H% values greater than 12%. Thehigher weight swell values are more comparable to chromium catalystproduced resins established in the market place.

EXAMPLE 3

The samples were generated to prepare resins having high molecularweight levels above 12% dry weight. These samples were prepared both ona laboratory scale and on a large scale in a pilot plant. Weight swellin these samples was increased significantly from the level of currentlycommercially available titanium catalyzed resins to levels close tothose of currently available chromium catalyzed resins, whilesignificantly lowering the VIS200, all by the addition of the highweight percent content levels of the high molecular weight componentwith constant blend MI₂.

                  TABLE 3                                                         ______________________________________                                                    H %        FSP      TW                                            Sample      H-MI.sub.2 (2.5)    (2.5)                                                                              VIS200                                   ______________________________________                                        A             13%-0.0027                                                      Lab                    37       1.23 0.87                                     Pilot Plant            51       1.21 0.94                                     B           23.4%-0.0027                                                      Lab                    42       1.30 0.83                                     Pilot Plant            47       1.37 0.79                                     C           18%-0.01.sup.                                                     Lab                    42       1.26 0.84                                     Pilot Plant            41       1.18 0.90                                     Ti-catalyst resin      44       1.04 1.08                                     Cr-catalyst resin      42       1.30 0.96                                     ______________________________________                                    

Commercial titanium and chromium catalyzed resins described above areincluded in Table 3 for comparative purposes. The table shows that thetube weight (TW) and flare swell percent (FSP) are improvedsignificantly over the levels of currently available titanium baseresins.

These results indicate that physical properties of resins obtained inthe lab agree fairly well with the properties of resins obtained in thepilot plant of the same composition. Thus, the results obtained in thelab constitute commercial scale resin properties.

In these cases, n-hexane was employed as the diluent in these reactorsas established in U.S. Pat. No. 4,223,118. The pressures of the threereactors were in the range of 10 to 140 psig. Hydrogen was added to thereactors at such a rate so as to keep the hydrogen to ethylene ratio inthe vapor space below 0.15. Temperatures in the reactors ranged from55°-90° C. Varying amounts of 1-butene were added to some of thereactors to control the density. These conditions typically producedresins like those given in the tables below. Table 4 gives thecompositions of the three samples while Table 5 briefly details theprocessing properties, as measured by laboratory tests, along withphysical properties (topload and drop impact strength) of bottles blownon intermittent blow molding equipment. ESCR was determined on bottlesmade on continuous blow molding equipment instead of intermittent blowmolding machines because they yielded more reproducible data and wereless dependent upon the processing conditions of bottle preparation.

In addition, two chromium based resins were tested for comparativepurposes, one (K) is made by Soltex Polymer Corp. while the other (L) ismade by Chemplex Co.

                  TABLE 4                                                         ______________________________________                                        Sample                                                                              H %     H-MW     M %   M-MW   L %   L-MW                                ______________________________________                                        H     20      642,000  33    134,000                                                                              47    67,500                              I     21      600,000  26    244,000                                                                              53    67,500                              J     18      860,000  34    106,000                                                                              48    55,000                              ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________                                       Drop                                                         Flare                                                                              Tube   Topload                                                                            Impact                                                  Density                                                                            Swell                                                                              Weight                                                                            Vis                                                                              Strength                                                                           Strength                                                                           Bottle                                Sample                                                                            MI.sub.2                                                                         MI.sub.20 /MI.sub.2                                                                 (g/cc)                                                                             Percent                                                                            g   200                                                                              (lbs)                                                                              (lbs)                                                                              SCR (hr)                              __________________________________________________________________________    H   0.51                                                                             99    0.958                                                                              47   1.47                                                                              0.77                                                                             66.3 13.4 14                                    I   0.47                                                                             89    0.958                                                                              54   1.31                                                                              0.84                                                                             68.3 16.3 11.8                                  J   0.38                                                                             71    0.957                                                                              52   1.28                                                                              1.1                                                                              68.6  32+ 19.2                                  K   0.40                                                                             88    0.954                                                                              41   1.26                                                                              0.93                                                                             56.6 17.1  5.0                                  L   0.39                                                                             95    --   41   1.29                                                                              0.91                                                                             58.2 12.5  8.3                                  __________________________________________________________________________

While certain embodiments and details have been shown for the purpose ofillustrating this invention, it will be apparent to those skilled inthis art that various changes and modifications may be made hereinwithout departing from the spirit or scope of the invention.

We claim:
 1. A polyethylene resin composition comprising high molecularweight, medium molecular weight and low molecular weight fractions,which are selected from the group consisting of homopolymers of ethyleneand copolymers of ethylene and/or olefins having three to twelvecarbons, wherein;(A) the molecular weight of the high molecular weightcomponent (H-MW) ranges from 590,000 to 860,000 and comprises 12 to 25percent by weight of the total resin; (B) the molecular weight of themedium molecular weight component (M-MW) ranges from about 75,000 toabout 600,000 and comprises 5 to 83 percent by weight of the totalresin; (C) the molecular weight of the low molecular weight component(L-MW) ranges from about 10,000 to about 100,000 and comprises 5 to 83percent by weight of the total resin; and wherein the ratio ofH-MW/M-MW≧1.7 and the ratio of M-MW/L-MW≧1.7, wherein the density of thetotal resin ranges from 0.940 to 0.970 and the melt index at a 2.16kilogram load ranges from about 0.01 to about 2.0.
 2. A composition asdescribed in claim 1 wherein component (A) comprises from 16 to 22percent by weight of the total resin.
 3. A composition as described inclaim 2 wherein component (B) comprises from 20 to 35 percent by weightof the total resin.
 4. A composition as described in claim 3 whereincomponent (C) comprises from 43 to 64 percent by weight of the totalresin.
 5. A composition as described in claim 4 wherein the density ofthe total resin ranges from 0.950 to 0.960.
 6. A composition asdescribed in claim 5 when prepared using Ziegler catalysts based ontitanium, vanadium or mixtures of these.
 7. A composition as describedin claim 6 wherein component (A) has a molecular weight range from about660,000 to about 775,000.
 8. A composition as described in claim 7wherein component (A) comprises from 16 to 22 percent by weight of thetotal resin.
 9. A composition as described in claim 8 wherein component(B) comprises from 20 to 35 percent by weight of the total resin.
 10. Acomposition as described in claim 9 wherein component (C) comprises from43 to 64 percent by weight of the total resin.
 11. A composition asdescribed in claim 10 wherein the density of the total resin ranges from0.950 to 0.960.